EP3776615B1 - Formulations chimiques pour dispositif électrochimique - Google Patents

Formulations chimiques pour dispositif électrochimique Download PDF

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EP3776615B1
EP3776615B1 EP19804061.0A EP19804061A EP3776615B1 EP 3776615 B1 EP3776615 B1 EP 3776615B1 EP 19804061 A EP19804061 A EP 19804061A EP 3776615 B1 EP3776615 B1 EP 3776615B1
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lithium
liquefied gas
electrolyte
salt
solvent
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EP3776615A1 (fr
EP3776615A4 (fr
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Cyrus Sam Rustomji
Yangyuchen YANG
Daniel Davies
Jungwoo Lee
Ying Shirley Meng
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University of California
South 8 Technologies Inc
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University of California
South 8 Technologies Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Electrochemical energy storage devices such as batteries and double layer capacitors, utilize an ionic conducting electrolyte solution to carry charge between positive and negative electrodes.
  • these electrolytes are a liquid at a standard room temperature of 20 °C and standard pressure (approximately 1.01325 bar).
  • the electrolyte solutions use a mixture of some amount of solvent and salt and additional components, or additives, for improved electrochemical stability of the device.
  • Common component additives include vinyl carbonate, fluoroethylene carbonate, lithium bis(oxalato)borate among others. Such additives help in surface modification of electrodes, safety aspects or in other useful ways. Solubility of salts is generally a function of the primary solvent, rather than additives.
  • the ionically conducing electrolyte of the preceding paragraph also comprises a solution of one or more solvents.
  • the liquefied gas electrolyte comprises a liquefied gas solvent.
  • the one or more solvents in exemplary electrochemical devices may be selected from the group consisting of liquefied gas solvents, liquid solvents, or solid solvents.
  • solid solvent as referring to a solvent, which is solid at room temperature, can form a liquid solution, when mixed with other liquid or liquids.
  • the solution of one or more solvents may be a solution of one or more liquefied gas solvents.
  • any single component of liquefied gas solvents may have a vapor pressure above an atmospheric pressure at room temperature
  • the mixture of any number of liquefied gas solvents, any number of additives, any number of solvents, and any number of salts may also lower the vapor pressure of the full solution to below an atmospheric pressure at room temperature.
  • the solution of one or more liquefied gas solvents may have a vapor pressure above or below an atmospheric pressure at room temperature.
  • the ionically conducing electrolyte comprises one or more additives (or additive components).
  • the one or more additive components may be liquid, solid, or gas at standard room temperature of +20 °C and standard pressure (approximately 1.01325 bar).
  • the additive comprises tetrahydrofuran in equal molar ratio to the salt in a liquefied gas solvent solution such as fluoromethane with a LiTFSI salt.
  • electrochemical device may further comprise a housing, enclosing the ionically conducting electrolyte and structured to provide a pressurized condition to the one or more salts and the solution of one or more solvents, such as liquefied gas solvents, and a pair of electrodes in contact with the ionically conducting electrolyte.
  • a housing enclosing the ionically conducting electrolyte and structured to provide a pressurized condition to the one or more salts and the solution of one or more solvents, such as liquefied gas solvents, and a pair of electrodes in contact with the ionically conducting electrolyte.
  • the electrochemical device is an electrochemical energy storage device as described in PCT/US2014/066015 and PCT/US2017/029821 , which are incorporated by reference in their entireties.
  • the electrochemical device is a rechargeable battery, ultracapacitor, or supercapacitor.
  • the rechargeable battery may be a lithium ion battery or a lithium metal battery.
  • the ionically conducting electrolyte can be composed of solvents and salts, wherein the solvents further comprise of only materials which are gaseous under standard conditions.
  • the materials included fluoromethane, difluoromethane and carbon dioxide.
  • additional additives are used that provide a beneficial use as it relates to improved salt solubility in solution.
  • Embodiments relate to material additives which increase the solubility of an electrolyte salt component. Without such additives, the solubility of the salt may be limited.
  • additives may be treated as an additional component to the overall solvent solution.
  • Salt solubility is primarily a function of the binding energy between positively and negatively charged ions, binding energy between positively charged ions and the solvent, and binding energy between negatively charged ions and the solvent. These binding energies are a function of temperature and particular ions and solvents in solution. When binding energy between positively and negatively charged ions is low compared to binding energy between ions and solvent molecules, the salt has higher solubility within the solvent. This is due to the solvents ability to effectively separate the positively and negatively charged ions and overcome their respective coulombic attraction, which allows ions to solubilize in solution without coming into contact with oppositely charged ions in solution. When binding energy between positively and negatively charged ions is high compared to binding energy between ions and solvent molecules, the salt has lower solubility within the solvent. This is due to the solvents inability to effectively separate the positively and negatively charged ions to overcome their respective coulombic attraction, which results in positive and negative ions coming into contact and separating out of solution, lowering overall solubility.
  • Figure 8 demonstrates a situation where the binding energy between salt ions is larger than that between ions and solvent.
  • solvent molecule 1 is generally attracted to positive ion 3 and so several solvent molecules 1 will form a solvation shell around positive ion 3.
  • Binding energy of the negative ion and the solvent in this example is considered to be low and therefore neglected here.
  • four solvent molecules surround the ion in the immediate solvation shell.
  • the binding energy between positive ion 3 and all the solvent molecules in the solvent shell is comparatively low to the binding energy between positive ion 3 and negative ion 4.
  • the binding between these molecules are represented by a solid line for binding between positive ion 3 and solvent 1 and a dashed line for binding between positive ion 3 and negative ion 4.
  • the summation of all binding energy with solvent on a single positive ion represented by solid lines is comparably lower than the binding energy between positive ion 2 and negative ion 4, represented by the dashed line. This allows the ions to stay in contact and lowers the solubility of the salt in solution.
  • Figure 9 demonstrates a situation where the binding energy between salt ions is smaller than that between ions and solvent.
  • solvent molecule 1 is generally attracted to positive ion 3 and so several solvent molecules 1 will form a solvation shell around positive ion 3. Binding energy of the negative ion and the solvent in this example is considered to be low and therefore neglected here.
  • the solvent solution is composed of an additional additive 5 in equal molar quantity as the salt. This additive has higher binding energy with the positive ion 3 than does the other solvent molecule 1.
  • the binding between solvent 1 and positive ion 3 is represented by a solid line whereas binding between additive 5 and positive ion 1 is represented by long dash line 2.
  • the solvation shell is composed of four solvent molecules total around a single positive ion 3, however, now the solvent shell is composed of two different types of molecules.
  • the binding energy between positive ion 3 and all the solvent molecules in the solvent shell is comparatively high to the binding energy between positive ion 3 and negative ion 4.
  • the summation of all binding energy with solvent on a single positive ion represented by solid lines and long dashed lines is comparably higher than the binding energy between positive ion 2 and negative ion 4, represented by the dashed line. This allows for increased separation between ions and higher solubility of the salt into solution.
  • Temperature has an influence on binding energy of various materials and so solubility may increase or decrease with temperature. Further, although average binding energies of the ions comprising a salt may be higher or lower than binding energies between ions and solvent molecules, random statistical fluctuations due to kinetic movement of molecules or alignment of molecules will generally show some minor solubility of components in solutions that are generally considered insoluble and generally show some minor salt precipitation in solutions that are generally considered soluble.
  • ion aggregates are formed. This is when two or more ions of same or differing charge come into contact and form a stable particle in solution. For example, two positively charged ions and a single negatively charged aggregate may for a single larger positively charged ion. Further, a single ion may have double or triple charge, such as often seen with magnesium or aluminum ions. While they are composed of larger aggregates, these ions are often still soluble in solution and may contribute to electrolytic conductivity of the electrolyte solution.
  • LiTFSI salt with moderate solubility
  • an electrolyte comprised of LiTFSI salt in fluoromethane and carbon dioxide solvent solution, which is a liquefied gas electrolyte. Since the binding energy of the solvent to the ions is comparably low to the binding energy of the Li cation and the TFSI anion, the LiTFSI salt has limited solubility in the solvent.
  • additive concentration may be higher or lower than the concentration of the salt.
  • a combination of additives or salts may be used in any respective molar ratios.
  • One advantage to limiting the additive concentration to less than or equal to the molar ratio of the salt is improved electrochemical stability of the additive. It has been shown in the literature that electrolyte solutions with high concentration of salts show increased electrochemical stability. This is because most or all solvent molecules are strong bound to a salt ion. This binding to a salt ion decreases the chemical reactivity of the solvent with the electrodes which causes decomposition. Generally, a free solvent molecule which is not bound to a salt ion will show decreased electrochemical stability.
  • an additive such as tetrahydrofuran is used in equal molar concentration with LiTFSI in fluoromethane. Since fluoromethane is a solvent with excellent electrochemical stability, the tetrahydrofuran is the most likely component to first undergo decomposition at an electrode surface. However, since the tetrahydrofuran is in equal molar concentration with the salt, nearly all tetrahydrofuran molecules are bound to the salt component at all times.
  • the tetrahydrofuran in fluoromethane based electrolyte behaves as if it is in a highly concentrated electrolyte since all tetrahydrofuran molecules are coordinated with or bound to a salt ion, thus lowering decomposition reactions with electrodes and improving electrochemical stability.
  • a mixture of one solvent and one additive with a salt will form a soluble and miscible solution.
  • another solvent or additive causes the solution to separate and become non-miscible.
  • An example of this would be the mixture of 0.3M LiTFSI and 0.3 tetrahydrofuran in liquefied gas fluoromethane which shows good miscibility and solubility for all components.
  • a mixture of 0.3M LiTFSI and 0.3 tetrahydrofuran in a solution of two parts by volume fluoromethane and one part by volume sulfuryl fluoride, also a liquefied gas solvent shows a distinct separation of components from solution.
  • the liquefied gas solvents can be difluoromethane. In some embodiments, the liquefied gas solvents can be chloromethane. In some embodiments, the liquefied gas solvents can be 1,1-difluoroethane. In some embodiments, the liquefied gas solvents can be sulfuryl fluoride. In some embodiments, the liquefied gas solvents can be thionyl chloride or thionyl fluoride. In some embodiments, the liquefied gas solvents can be selected from the group consisting of fluoromethane, difluoromethane, sulfuryl fluoride, chloromethane, carbon dioxide, 1,1-difluoroethane and any combination thereof.
  • the liquefied gas electrolyte includes a single liquefied gas solvent or a combination of liquefied gas solvents and one or more additive and one or more salt.
  • additives may be gaseous, liquid or solid at standard room temperature of +20 °C and standard pressure (approximately 1.01325 bar). Further, any of the gaseous additives may also be used as primary solvent.
  • the amount of the primary solvent or mixture of primary solvents is greater than about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, about 98%, or about 99% by weight based on the total weight of the liquefied gas electrolyte.
  • the amount of the primary solvent is less than about 99%, about 98%, about 95%, about 90%, about 80%, about 70%, about 60%, about 50%, about 40%, about 30%, or about 20% by weight based on the total weight of the liquefied gas electrolyte.
  • the amount of the additive is less than about 80%, about 70%, about 60%, about 50%, about 40%, about 30%, about 20%, about 10%, about 5%, about 2%, or about 1% by weight based on the total weight of the liquefied gas electrolyte.
  • the liquefied gas solvents comprise halogenated hydrocarbon and sulfuryl halide. In some embodiments, the liquefied gas solvents comprise halogenated hydrocarbon, sulfuryl halide, and carbon dioxide. According to the invention as set forth with independent claim 1, the molar ratio of salt to additive is between 0.3 and 3.0.
  • the molar ratio of the additive to the salt is greater than about 0.01, about 0.05, about 0.1, about 0.2, about 0.30, about 0.5, about 0.7, about 0.9, about 0.95, about 0.98, about 1.0, about 1.05, about 1.1, about 1.5, about 2, about 3, about 5, about 10, or about 100.
  • having a lower molar concertation additive as compared to salt such of about 0.9, about 0.95, or about 0.98 may be favorable in order to guarantee that the majority of additive material in the electrolyte generally is binding or coordinated to an ion in the electrolyte, thus increasing electrochemical stability of the cell.
  • having a higher molar concertation additive as compared to salt such of about 1.1, about 1.2, or about 2.0 may be favorable in order to guarantee maximum solubility of salt for improved performance.
  • multiple additives are used, each of which may have molar ratio to the salt is greater than about 0.01, about 0.05, about 0.1, about 0.2, about 0.30, about 0.5, about 0.7, about 0.9, about 0.95, about 0.98, about 1.0, about 1.05, about 1.1, about 1.5, about 2, about 3, about 5, about 10, or about 100.
  • the salt concentration in the electrolyte solution is greater than about 0.1, about 0.3, about 0.5, about 0.8, about 1.0, about 1.3, about 1.5, about 1.8, about 2.0, about 3.0, about 4.0, about 5.0, or about 8.0 moles per liter of solution.
  • the liquefied gas electrolyte can include one or more additives. In some embodiments, the liquefied gas electrolyte can include one additive. In some embodiments, the liquefied gas electrolyte can include two or more additives. In some embodiments, the additive can be a noncyclic carbonate, a cyclic carbonate, a non-cyclic ether, a cyclic ether, or a nitrile compound, or any combination thereof. In some embodiments, the additive is tetrahydrofuran.
  • the electrodes are composed of any combination of two electrodes of intercalation type such as graphite, carbon, activated carbon, lithium titanate, titanium disulfide, molybdenum disulfide, lithium iron phosphate, lithium cobalt phosphate, lithium nickel phosphate, lithium cobalt oxide, lithium nickel manganese oxide, lithium nickel manganese cobalt oxide, lithium nickel cobalt aluminum oxide or chemical reaction electrode such as with chemicals of sulfur, oxygen, carbon dioxide, nitrogen, sulfur dioxide, thionyl fluoride, thionyl chloride fluoride, sulfuryl fluoride, sulfuryl chloride fluoride or of a metallic electrode with lithium metal or sodium metal or metal alloy including lithium, sodium, tin, aluminum, or any combination thereof.
  • these components may be combined with various binder polymer components including polyvinylene glycol, polyethylene glycol, sodium carbon oxide, sodium, tin, aluminum, or any combination thereof.
  • the one or more liquefied gas solvent solution or electrolyte may be combined with one or more salts including one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium tetrachloroaluminate, lithium tetragaliumaluminate, lithium bis(oxalato)borate, lithium hexafluorostannate, lithium difluoro(oxalato)borate, lithium bis(fluorosulfonyl)imide, lithium aluminum fluoride, lithium chloroaluminate, lithium tetrafluoroborate, lithium tetrachloroaluminate, lithium difluorophosphate, lithium tetrafluoro(oxalato)phosphate, lithium difluorobis(oxalato)phosphate, lithium borate, lithium oxolate, Li
  • Figure 1 shows the solubility of the salt lithium bis(trifluoromethanesulfonyl)imide in fluoromethane at a concentration of 0.3 moles salt per liter (0.3 M) at room temperature. The majority of salt remains non-dissolved. However, it is known a small amount of salt does dissolve at concentrations less than 0.3 M to form a conductive solution since functional battery devices have been constructed and show high performance. In order to improve solubility of salts, an additional additive may be added to solution to improve salt disassociation.
  • Example 2 Similar to Example 1, several additional additives in place of tetrahydrofuran have been used to improve solubility of LiTFSI in fluoromethane; select additives that are tested include acetonitrile, ethylene carbonate, dimethyl carbonate, dimethoxyethane, fluoroethylene carbonate, among several others. Salt concentrations in these experiments vary from 0.1 M to 1M with high solubility of LiTFSI and the additive in equal molar concentration in fluoromethane. These solutions generally showed high solubility and good miscibility without phase separation from temperatures as low as -78 °C up to around + 40 °C where two phase separation may occur in some instances.
  • a lithium metal anode could substantially increase the energy density of battery devices, however, require a significant improvement in efficiency to make a useful device.
  • Cells composed of a lithium metal electrode and a stainless steel counter electrode were built and used to test lithium metal plating and stripping efficiency of lithium metal. Electrolyte solutions of 0.3M LiTFSI and 0.3M tetrahydrofuran in 19 parts by volume fluoromethane and 1 part by volume carbon dioxide were used. These cells were used to plate 0.5 mAh/cm2 lithium metal onto the stainless steel working electrode at a current of 0.5 mA/cm2 at room temperature over several hundred cycles. A high voltage cutoff of 1V is used for a stripping limit, upon when the current is reversed, and plating resumed.
  • solubility lithium salts were examined in sulfuryl fluoride, a mixture of fluoromethane and sulfuryl fluoride, and mixtures of fluoromethane, sulfuryl fluoride with a THF additive.
  • the solubility was visually examined via high pressure sight glass window.
  • Figure 11 shows the solubility of the salt lithium bis(trifluoromethanesulfonyl)imide in sulfuryl fluoride at a concentration of 0.1 moles salt per liter (0.1 M) at room temperature.

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Claims (8)

  1. Dispositif électrochimique rechargeable, comprenant :
    un électrolyte à gaz liquéfié conducteur de manière ionique comprenant un solvant de gaz liquéfié et un sel de lithium ;
    un boîtier renfermant l'électrolyte à gaz liquéfié et structuré pour fournir une condition pressurisée à l'électrolyte à gaz liquéfié ; et
    au moins deux électrodes conductrices en contact avec l'électrolyte à gaz liquéfié ;
    l'électrolyte à gaz liquéfié fonctionnant à une pression de vapeur supérieure à une pression atmosphérique de 100 kPa à une température ambiante de 293,15 K ;
    l'électrolyte à gaz liquéfié étant capable d'être placé sous une pression de compression égale à, ou supérieure à, la pression de vapeur du solvant de gaz liquéfié à température ambiante lorsque la pression de compression est appliquée, maintenant ainsi l'électrolyte à gaz liquéfié dans une phase liquide ; et
    l'électrolyte à gaz liquéfié restant dans une phase liquide unique à 293 K ;
    l'électrolyte à gaz liquéfié comprenant en outre un ou plusieurs additifs, fournissant ainsi l'électrolyte à gaz liquéfié en combinaison avec le solvant de gaz liquéfié et le sel de lithium ;
    l'additif ou les additifs étant choisis dans le groupe constitué par : des carbonates cycliques, des carbonates non cycliques, des éthers cycliques, des éthers non cycliques et des nitriles ;
    le rapport molaire du sel de lithium sur l'additif étant compris entre 0,3 et 3,0, moyennant quoi le sel de lithium est soluble jusqu'à au moins 0,4 M dans l'électrolyte à gaz liquéfié ; et
    l'électrolyte à gaz liquéfié ayant une conductivité d'au moins 3,5 mS/cm à 293 K.
  2. Dispositif électrochimique rechargeable selon la revendication 1, le solvant de gaz liquéfié comprenant une ou plusieurs matières choisies dans le groupe constitué par : fluorométhane, difluorométhane, fluorure de sulfuryle, chlorure de sulfuryle, dioxyde de carbone, 1,1-difluoroéthane, chlorométhane, oxyde nitreux et une combinaison correspondante.
  3. Dispositif électrochimique rechargeable selon l'une quelconque des revendications 1 et 2, l'additif ou les additifs comprenant de l'acétonitrile, du tétrahydrofuranne et/ou de l'éther méthylique.
  4. Dispositif électrochimique rechargeable selon l'une quelconque des revendications 1 à 3, le dispositif électrochimique étant une batterie, un ultracondensateur ou un supercondensateur rechargeable.
  5. Dispositif électrochimique rechargeable selon la revendication 4, la batterie rechargeable étant une batterie lithium ion ou une batterie lithium métal.
  6. Dispositif électrochimique rechargeable selon l'une quelconque des revendications 1 à 5, les électrodes comprenant l'un ou plusieurs parmi le graphite, le carbone, le carbone activé, le titanate de lithium, le disulfure de titane, le disulfure de molybdène, le phosphate de fer de lithium, le phosphate de cobalt de lithium, le phosphate de nickel de lithium, l'oxyde de cobalt de lithium, l'oxyde de manganèse de nickel de lithium, l'oxyde de cobalt de manganèse de nickel de lithium et l'oxyde d'aluminium de cobalt de nickel de lithium.
  7. Dispositif électrochimique rechargeable selon l'une quelconque des revendications 1 à 6, les électrodes étant des électrodes métalliques et comprenant l'un ou plusieurs parmi le lithium métal, le sodium métal ou un alliage métallique comprenant du lithium, du sodium, de l'étain, de l'aluminium, ou une quelconque combinaison correspondante.
  8. Dispositif électrochimique rechargeable selon la revendication 6 ou la revendication 7, les électrodes comprenant en outre divers composants polymères de liant choisis dans le groupe constitué par : poly(fluorure de vinylidène), carboxyméthylcellulose, caoutchouc de styrène-butadiène et polytétrafluoroéthylène.
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113675475A (zh) * 2019-04-26 2021-11-19 宁德时代新能源科技股份有限公司 电解液及锂离子电池
CA3214832A1 (fr) * 2019-09-30 2021-04-08 South 8 Technologies, Inc. Formulations electrolytiques pour dispositif electrochimique
CN110931875B (zh) * 2019-12-24 2023-02-07 哈尔滨工业大学 一种耦合有机锂盐和氟代碳酸乙烯酯的丁二腈基电解液、制备方法及其应用
WO2022256320A1 (fr) * 2021-06-01 2022-12-08 South 8 Technologies, Inc. Additifs chimiquement inertes pour cellules électrochimiques
KR20220163578A (ko) * 2021-06-03 2022-12-12 주식회사 엘지에너지솔루션 리튬-황 전지용 전해액 및 이를 포함하는 리튬-황 전지
WO2023196489A1 (fr) * 2022-04-07 2023-10-12 South 8 Technologies, Inc. Électrolytes de gaz liquéfié à pression de vapeur réduite utilisant un sel à haute concentration
US12080851B1 (en) 2023-03-08 2024-09-03 South 8 Technologies, Inc. Electrolyte chemical formulations for energy storage devices

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3069401B1 (fr) * 2013-11-15 2018-11-07 The Regents of the University of California Dispositifs électrochimiques comprenant des électrolytes à base de solvant de type gaz comprimé

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2310080A (en) 1940-01-08 1943-02-02 Gen Motors Corp Nonoverfill device
US3540929A (en) 1969-05-05 1970-11-17 Gen Electric Deep submergence rechargeable sealed secondary cell
US4460666A (en) 1981-11-24 1984-07-17 Dinkler Leonard R Coated substrate, preparation thereof, and use thereof
DE3920129A1 (de) * 1988-06-21 1989-12-28 Ricoh Kk Elektrochemische vorrichtung
US5213908A (en) 1991-09-26 1993-05-25 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Alkali metal carbon dioxide electrochemical system for energy storage and/or conversion of carbon dioxide to oxygen
US5770033A (en) 1993-07-13 1998-06-23 Lynntech, Inc. Methods and apparatus for using gas and liquid phase cathodic depolarizers
JP3581474B2 (ja) 1995-03-17 2004-10-27 キヤノン株式会社 リチウムを利用する二次電池
US5753389A (en) * 1995-03-17 1998-05-19 Wilson Greatbatch Ltd. Organic carbonate additives for nonaqueous electrolyte in alkali metal electrochemical cells
US20010049051A1 (en) 1996-11-12 2001-12-06 William E. M. Jones Use of catalysts in standby valve-regulated lead acid cells
JP4038826B2 (ja) 1996-07-19 2008-01-30 宇部興産株式会社 非水電解液二次電池および製造法
EP1244168A1 (fr) 2001-03-20 2002-09-25 Francois Sugnaux Electrode à réseau mésoporeux pour batterie
US7513978B2 (en) 2003-06-18 2009-04-07 Phillip J. Petillo Method and apparatus for generating hydrogen
KR100515356B1 (ko) 2003-06-19 2005-09-15 삼성에스디아이 주식회사 이차 전지 및 이의 안전변 제조 방법
WO2004113443A1 (fr) * 2003-06-19 2004-12-29 Daiso Co., Ltd. Electrolyte polymere reticule et utilisation associee
KR101353363B1 (ko) 2005-01-18 2014-02-18 옥시스 에너지 리미티드 황 또는 황 화합물을 사용한 전지용 전해질 조성물에 관한개선
JP4967890B2 (ja) 2007-05-01 2012-07-04 トヨタ自動車株式会社 空気電池システム
DE102008005841A1 (de) 2008-01-24 2009-07-30 Forschungszentrum Jülich GmbH Hochtemperatur-Polymerelektrolyt Brennstoffzellensystem (HT-PEFC) sowie ein Verfahren zum Betreiben desselben
KR101041829B1 (ko) 2008-04-16 2011-06-17 주식회사 엘지화학 폴리아크릴로니트릴-아크릴산 공중합체 및 바인더를 포함한음극 재료 조성물, 그 제조방법 및 그 음극 재료 조성물을포함하는 리튬 이차 전지
DE102010049649A1 (de) 2010-10-28 2012-05-03 Carl Freudenberg Kg Magnetisch dichtende Ventilvorrichtung für ein Batteriegehäuse
EP2830141B1 (fr) 2012-03-19 2019-07-03 National University Corporation Yokohama National University Pile secondaire lithium-soufre
JP2015004152A (ja) 2013-06-24 2015-01-08 東レ・モノフィラメント株式会社 モノフィラメントおよびそれを用いてなるメガネフレーム
JP2015041526A (ja) 2013-08-22 2015-03-02 株式会社豊田自動織機 蓄電装置の蓋体とケース本体との溶接方法
TWI517482B (zh) 2015-02-16 2016-01-11 有量科技股份有限公司 鋰電池的排氣結構
US9958146B2 (en) 2015-07-17 2018-05-01 Cooper Technologies Company Low profile ceiling mounted luminaire
KR102050836B1 (ko) * 2015-12-08 2019-12-03 주식회사 엘지화학 리튬이차전지용 전해질 및 이를 포함하는 리튬이차전지
WO2017160588A1 (fr) * 2016-03-18 2017-09-21 Colorado State University Research Foundation Électrolyte multifonctionnel pour la gestion thermique de batteries au lithium-ion
US10868332B2 (en) * 2016-04-01 2020-12-15 NOHMs Technologies, Inc. Modified ionic liquids containing phosphorus
JP7226771B2 (ja) 2016-05-27 2023-02-21 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア 電気化学エネルギー貯蔵デバイス
US11258101B2 (en) * 2017-06-26 2022-02-22 Global Graphene Group, Inc. Non-flammable electrolyte containing liquefied gas and lithium secondary batteries containing same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3069401B1 (fr) * 2013-11-15 2018-11-07 The Regents of the University of California Dispositifs électrochimiques comprenant des électrolytes à base de solvant de type gaz comprimé

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JP7146219B2 (ja) 2022-10-04
US10784532B2 (en) 2020-09-22
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USRE50031E1 (en) 2024-07-02
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US20200067130A1 (en) 2020-02-27
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